kinetic and thermodynamic analysis of guaiacol hydrodeoxygenation … · 2019. 7. 4. · kinetic...

Kinetic and Thermodynamic Analysis of Guaiacol Hydrodeoxygenation

Alexandrina Sulman1 • Päivi Mäki-Arvela1 • Louis Bomont1 • Moldir Alda-Onggar1 • Vyacheslav Fedorov1 •Vincenzo Russo2 • Kari Eränen1 • Markus Peurla3 • Uliana Akhmetzyanova4 • Lenka Skuhrovcová4 •Zdeněk Tišler4 • Henrik Grénman1 • Johan Wärnå1 • Dmitry Yu. Murzin1

Received: 18 April 2019 / Accepted: 30 May 2019 / Published online: 12 June 2019� The Author(s) 2019

AbstractKinetics of guaiacol hydrodeoxygenation (HDO) was studied using supported MoxC–SBA-15 and as a comparison 5 wt%

Pt/C under 30 bar hydrogen at 200 �C and 300 �C. Catalyst characterization was done by a range of physical methodsincluding also determination of the amount of coke and the nature of adsorbed species. Pt/C gave 2-methoxycyclohexanol

as the main product, whereas Mo2C–SBA-15 promoted direct deoxygenation exhibiting also strong adsorption of guaiacol

on the catalyst surface and formation of oligomers. Thermodynamics of guaiacol HDO was elucidated and the reaction

network was proposed based on which kinetic modelling was done.

Graphic Abstract

OH

OCH3

OCH3

OH

OH

OH

CH3

1

2

7 3

5

8

6

guaiacol

cyclohexane

2-methoxycyclohexane

cyclohexanol

phenol

anisole

cresol

OCH3

OH

OCH3

2-methoxy-cyclohexanol

12

4

10

CH3

toluene

benzene

11

1314

16

OCH3

O

15

2-methoxy-cyclohexanone

9

(+methane)

17 (+guaiacol, -catechol)

Keywords Guaiacol � Hydrodeoxygenation � Carbide � Kinetics � Thermodynamics

List of SymbolsK0j Equilibrium constant at standard conditions for

reaction j

n Moles (mol)

P Pressure (bar)

P0 Standard pressure (bar)

R Ideal gas constant (J/K/mol)

T Absolute temperature (K)

T0 Absolute standard temperature (K)

& Dmitry Yu. [email protected]

1 Johan Gadolin Process Chemistry Centre, Åbo Akademi

University, Turku, Finland

2 Università di Napoli Federico II, Via Cintia, 4. IT-80126,

Naples, Italy

3 University of Turku, Turku, Finland

4 Unipetrol Centre for Research and Education (UniCRE),

Chempark Litvı́nov, Block 2838, 436 70 Litvı́nov-Zálužı́ 1,

Czech Republic

123

Catalysis Letters (2019) 149:2453–2467https://doi.org/10.1007/s10562-019-02856-x(0123456789().,-volV)(0123456789().,-volV)

http://orcid.org/0000-0003-0788-2643http://crossmark.crossref.org/dialog/?doi=10.1007/s10562-019-02856-x&domain=pdfhttps://doi.org/10.1007/s10562-019-02856-x

Greek SymbolsDG0f Gibbs free energy of formation at standard

conditions (J/mol)

DG0r Gibbs free energy of reaction at standardconditions (J/mol)

DGUr;j Gibbs free energy of reaction at 1 bar and a chosentemperature (J/mol)

DGr,j Gibbs free energy of reaction at a fixed temperatureand pressure (J/mol)

DH0f Enthalpy of formation at standard conditions(J/mol)

DH0r Enthalpy of reaction at standard conditions (J/mol)mi,j Stoichiometric matrix composed by i components

and j reactions (–)

1 Introduction

Biomass has been recently used as a cheap and abundant

raw material for production of fuels and chemicals, for

example via pyrolysing woody biomass and extraction of

lignin to obtain among other products large amounts of

phenolic compounds. Such compounds are not suitable di-

rectly as fuels due to their high oxygen content thus

requiring deoxygenation. Bio-oil obtained by wood pyrol-

ysis has a low pH, is unstable and contains some catalyst

poisons. Subsequently catalytic deoxygenation is far from

being straightforward. Upgrading of bio-oil and lignin

extracts via hydrodeoxygenation (HDO) is currently under

intensive research [1–26] with both real bio-oil as well as

model compounds used as a feedstock.

HDO of guaiacol in particular has been intensively

investigated recently using, for example, Fe/SiO2 [20],

Mo2N [3, 4], Mo2C/CNF [2, 13], MoC/AC [16], Mo2C/AC

[6], W2C/CNF [13], Ni/ZrO2 [23], NiP/SiO2 [25], ReOx[5], Au/TiO2 and Au–Rh/TiO2 [17], Pt/C [8], Pt/alumina

silicate [10], PtPd–Al–HMS [26], PtPd–ZrO2–SiO2, [26]

Ru/C [1], Ru–TiO2–ZrO2 [15], Rh/ZrO2 combined with

alumina silicate [12] as catalysts. HDO is a complex pro-

cess involving several parallel and consecutive reaction

steps, e.g. demethoxylation (1, 11, 16), dehydroxylation (2,

8, 13, 14), alkylation (4) and hydrogenation (3, 7, 12, 15)

(Scheme 1; Table 1). Scheme 1 contains different reac-

tions, which can be present during HDO depending on the

reaction conditions and catalysts. For example, formation

of cresol from phenol can occur through alternative path-

ways (methanation, reaction 4) and transalkylation with

guaiacol giving cresol and catechol (reaction 17). The

latter reaction proceeds through a surface methoxide

intermediate.

The benefits of using carbides and nitrides as catalysts

are their lower prices, moreover nitrides and carbides

exhibit also metal-like properties [27]. However, synthesis

of carbides and nitrides requires high temperatures, in the

OH

OCH3

OCH3

OH

OH

OH

CH3

1

2

7 3

5

8

6

guaiacol

cyclohexane

2-methoxycyclohexane

cyclohexanol

phenol

anisole

cresol

OCH3

OH

OCH3

2-methoxy-cyclohexanol

12

4

10

CH3

toluene

benzene

11

1314

16

OCH3

O

15

2-methoxy-cyclohexanone

9

(+methane)

17 (+guaiacol, -catechol)

Scheme 1 Reaction scheme for guaiacol transformation based on [4, 12–14]

2454 A. Sulman et al.

123

range of 700–1000 �C, giving typically materials with lowspecific surface area. For this reason, also supported car-

bides have been recently prepared and tested as catalysts

[3, 13].

Guaiacol HDO is typically performed in the temperature

range of 250–50 �C under hydrogen pressure varying from20 to 55 bar (Table 2) [1, 4, 5, 10, 12–14, 17, 24].

The results show that the main product is phenol when

molybdenum and tungsten carbides are used as catalysts

[4, 13], whereas supported Ni and ReOx catalysts gave

cyclohexane as the main product [5, 24]. Several metal

supported catalysts, such as TiO2–Pd–SiO2, Rh/ZrO2 and

Au–Rh/TiO2 afforded also the deoxygenated product,

cyclohexane [12, 14, 17], whereas Pt/C catalyzed only

phenyl ring hydrogenation giving 2-methoxycyclohexanol

as the main product [10].

Because catalyst deactivation can be a serious issue in

HDO of lignin derived substituted phenols, a special

emphasis in the current work was put on the mass balance

closure. The latter is typically represented through the sum

of the masses of reactant and products in the liquid phase

determined by GC. Another issue related to the mass bal-

ance closure is analysis of the spent catalyst giving, in

particular, information about adsorption of organic com-

pounds on the catalyst surface and coking. Coke analysis

has been scarcely reported in guaiacol HDO [8, 19, 25].

One example is temperature programmed oxidation of

spent Ni2P/SiO2 catalyst showing formation of CO and

CO2 mostly at ca. 460 �C [25]. Thermogravimetric analysisperformed for the spent catalyst used in the gas-phase

guaiacol HDO can be also mentioned showing ca. 20%

weight loss in the case of Pt/C catalyst [8]. Coke was also

estimated in gas phase HDO of guaiacol using Ni- and Fe-

based commercial catalysts [19]. In the current work size

exclusion chromatography (SEC) was used to qualitatively

confirm the presence of oligomers. Even if oligomer

analysis has been applied very rarely in the literature, one

example related to HDO of bio-oil is worth mentioning

[31] when gel permeation chromatography was utilized to

analyze macromolecules.

Kinetics of guaiacol transformation in batch reactors has

been very scarcely reported including reactions over W2C/

CNF, Mo2C/CNF [13], Mo2N [3] and ReOx [5]. From the

discussion above it can be concluded that while molybde-

num nitride and carbide have been used in guaiacol HDO,

the literature is void from the data for supported Mo2C on

Table 1 Different reactions in Scheme 1

Entry Reaction Entry Reaction1 OH O

CH3+ H2 CH3OH

OH

+

9O

CH3

OOH

OCH3 + 2H2

2 OH

+ H2 + H2O

10 OHO

CH3+ H2O

CH3

O

3+ 3H2

11 OHO

CH3

OH

CH3OH++ H2

4 OH

+ CH4

OH

CH3

+ H2

12 OHO

CH3+ H2O+ 3H2

OH

OCH3

5 OH

CH3

+ H2CH3

+ H2O

13 OHO

CH3

OCH3 + H2O+ H2

6

CH3

+ CH4+ H214

+ H2OH

OCH3

OCH3 + H2O

7 OH OH

+ 3H2

15 + 3H2O

CH3

OCH3

8 OH

+ H2 + H2O

16 O CH3 CH3OH++ H2

17

O

OH OH

+

OH

OH

OH

+

Kinetic and Thermodynamic Analysis of Guaiacol Hydrodeoxygenation 2455

123

mesoporous supports. The aim in this work was thus to

investigate kinetics of guaiacol transformation over

40 wt% Mo2C/SBA-15 prepared from hexamethylenete-

tramine ammonium heptamolybdate as a precursor.

Mesoporous silica SBA-15 with the cavity size larger than

6 nm [28] was selected as it can be expected that Mo2C

would be well dispersed affording easier diffusion of the

reacting molecules to the active sites. Mo2C/SBA-15 has

been prepared previously from MoO3/SBA-15 via the

temperature programmed carburization method [29].

The novelty in this work regarding the materials is that

Mo2C/SBA-15 has been prepared using hexamethylenete-

tramine ammonium heptamolybdate complex as a precur-

sor while this precursor has been earlier used in the

synthesis of Mo2C [30]. According to our knowledge

Mo2C/SBA-15 has not been investigated as a catalyst in

HDO of phenolic lignin derived model compounds. As a

benchmark catalyst Pt/C was used to compare its behavior

with molybdenum carbide. In addition to kinetic studies

also thermodynamics of guaiacol HDO, not previously

reported, was explored using the Gibbs–Helmholtz equa-

tion [32].

2 Experimental

Mesoporous silica with the SBA-15 structure was synthe-

sized following the method reported by Zukal et al. [33].

Tetraethyl orthosilicate (TEOS) was used as a silica source;

amphiphilic triblock copolymer P123 was applied as a

structure directing agent. Synthesis of SBA-15 was

performed at 95 �C during 66 h. The resulting solid wasrecovered by filtration, extensively washed with distilled

water and dried at 80 �C overnight. The template wasremoved by calcination in air at 540 �C for 8 h (with thetemperature ramp of 1 �C/min). Calcined extrudates werecrushed using a laboratory jaw crusher and sieved to obtain

a fraction 560 to 850 lm (Retsch AS 300).The supported catalyst was prepared by the incipient

wetness impregnation method from hexamethylenete-

tramine molybdate complex (HMT–AHM). The latter was

synthesized according to the method reported by Afanasiev

[34], who dissolved 86 g of hexamethylenetetramine

(HMT) and 50 g of ammonium heptamolybdate (AHM) in

400 mL and 300 mL distilled water, respectively. There-

after, these solutions were mixed and the final solution was

left in air at ambient conditions overnight resulting in

precipitation of crystals. These crystals were filtered using

a filter paper and washed with deionized water, followed by

drying in air at ambient temperature for 3 days. The

incipient wetness method was used to impregnate the

HMT–AHM precursor on the support (2 g SBA-15) fol-

lowed by drying at 120 �C overnight. This catalyst wascarburized with the same method as described above.

Temperature programmed reduction was done in the

flow of a gas mixture of 20 vol.% CH4 in H2 (the flow rate

75 mL/min) during 3 h at 700 �C (the temperature ramp of10 �C/min) with further passivation of the final materialwith the mixture of 1 vol.% O2 in Ar (75 mL/min during

2 h).

40 wt% MoxC–SBA-15 was reduced in pure H2 (flow

rate * 50 mL/min) at 450 �C (heating rate 5 �C/min) for

Table 2 Literature data on guaiacol hydrodeoxygenation

Catalyst Solvent T

(�C)Pressure

(bar)

Conversion (%)/time (h) Main product Yield, Y (%) or

selectivity, S (%)

References

W2C/CNF Dodecane 350 55 88/6 Phenol S = 49 [13]

Mo2C/CNF Dodecane 350 55 100/6 Phenol S = 38 [13]

MoN/C Decalin 300 50 48/6 Phenol Y = 28 [4]

Mo/C No solvent 350 40 92/Continuous mode, space

time = 0.068 h

Phenol Y = 45 [1]

Ni/SiO2–

ZrO2

Dodecane 300 50 88/5 Cyclohexane S = 90 [24]

ReOx/CNF Dodecane 300 50 98/6 Cyclohexane Y = 65 [5]

Pt/C Hexadecane 259 30 87/1 2-

Methoxycyclohexanol

Y = 80 [10]

TiO2–Pd/

SiO2

Dodecane 300 20 100/Continuous mode, weight

hour space velocity = 24 h-1Cyclohexane Y = 63 [14]

Au–Rh/TiO2 Gas phase 280 40 94/Continuous mode Cyclohexane Y = 62 [17]

Rh/ZrO2–

alumino

silicate

Decane 310 40 Not determined Cyclohexane Y = 68 [12]


123

13 h and cooled down to 170 �C under H2 flow and flushedwith Ar for 5 min. About 10–15 g of a solvent was intro-

duced to the reduced catalyst under Ar flow to avoid oxi-

dation. The catalyst was stored in the solvent overnight

prior to its use.

2.1 Catalyst Characterization Methods

Thermogravimetric analysis of the fresh and the spent

catalysts was performed under nitrogen using SDT Q600

(V20.9 Build 20) instrument. About 6–8 mg of the sample

was weighed, put in a platinum pan and heated from room

temperature to 625 �C with a 10 �C/min ramp. The purgegas feed rate into the system was 100 mL/min.

The synthesised catalyst was characterized by X-ray

powder diffraction (XRD) analysis performed with X-ray

diffractometer D8 Advance Eco (Bruker AXS) equipped

with SSD 160 detector using Cu Ka emission atk = 1.54 Å. XRD patterns were collected in the range of2h values from 5� to 70� (0.021�/step, integration time of0.5 s per step). The X-ray tube voltage was set to 40 kV

and the current to 25 mA. Diffraction data were evaluated

using the Diffrac.Eva V 4.1.1 software. Subsequently,

crystalline phases were identified according to the Powder

Diffraction database of the International Centre for

Diffraction Data (ICCD PDF2).

The textural properties were characterized by N2-ad-

sorption (BET) at 77 K performed with the gas sorption

analyzer—Autosorb-iQ (Quantachrome Instruments).

In order to examine the catalyst morphology transmis-

sion electron microscopy (TEM) using JEM 1400 plus

(JEOL) was applied. The acceleration voltage of 120 kV

and the resolution of 0.98 nm for Quemsa II MPix bottom

mounted digital camera were used. Scanning electron

microscopy (Zeiss Leo Gemini 1530) was used to deter-

mine the crystal morphology.

Ammonia TPD was performed using Autochem 2910

with the following temperature program: heating to 450 �Cfor 1 h, flushing the catalyst at 450 �C with helium, coolingto 100 �C—ammonia adsorption at 100 �C for 60 min,flushing chemisorbed ammonia away with helium flow at

100 �C and then starting the temperature ramp 10 �C/minto 900 �C. The outlet was connected to MS recording theresponse from ammonia, water and CO.

Coke was extracted from the selected spent catalysts

using heptane as a solvent similar to [35]. The extraction

was performed by refluxing the catalyst, 10 mg in heptane

solution, 10 mL, for 4 h under stirring.

2.2 Catalytic Tests and Analysis of ReactionMixture

The reactions were carried out in 300 mL batch reactor

(Parr Instruments) equipped with a stirrer and a sampling

line (with a 5 lm filter in order to take only the liquid fromthe reactor) and cooling water circulation. The reactor was

surrounded by an electrical heater. Argon (AGA 99.999%)

and hydrogen (AGA 99.999%) gas bottles were coupled to

the reactor system. The stirring speed during the reaction

was 900 rpm to avoid external mass transfer limitations.

In a typical experiment the liquid volume was 50 mL,

dodecane was used as a solvent together with 100 mg of

the reactant and 50 mg of a catalyst. Two temperature

levels, 200 �C and 300 �C were selected for investigationswhile the total pressure of 30 bar was used in all experi-

ments. Hydrogen partial pressures were at 200 �C and300 �C 29.3 bar and 24.8 bar, respectively.

40 wt% MoxC/SBA-15 was pre-reduced prior to

experiments, while the commercial reference catalyst

5 wt% Pt/C (Degussa, F106, XKYF/W) was used without

any prereduction. Total pressure of 30 bar was used also in

the latter case.

The samples taken at different times from the reactor

were analyzed by gas chromatography using DB-1 capil-

lary column (Agilent 122-13e) with the length of 30 m,

internal diameter of 250 lm and the film thickness of0.50 lm. The flow rate of helium was 1.9 mL/min. Thefollowing temperature program was used: at 60 �C thetemperature was held for 5 min, followed by ramp of 3 �C/min until 300 �C, where it was maintained for 1 min. Thefollowing chemicals were used in the experiments and

quantification of the reaction products: guaiacol (Fluka,

C 98%), (1S,2S)-2-methoxycyclohexanol (Aldrich),

methoxycyclohexane (Tokyo Chemical Industry Co.,

C 98%), 2-methoxycyclohexanone (Tokyo Chemical

Industry Co.,[ 95%), cyclohexanol (Sigma Aldrich,99%), phenol (Sigma Aldrich, 99%), cyclohexane (Lab-

Scan, 99%), cresol (Sigma Aldrich,[ 98%), anisole(Sigma Aldrich,[ 99%), 2-methoxy-4-methylphenol(Sigma Aldrich,[ 98%) and benzene (Sigma Aldrich,[99%). The unknown reaction products were identified

with GC–MS using a similar column and a method used

with GC.

Conversion of guaiacol was defined as:

X ¼ c0;G � ci;Gc0;G

� 100%; ð1Þ

were X is conversion and c0,G and ci,G are the concentra-

tions of guaiacol at the beginning and at time t. The product

selectivity (or molar fraction) is defined as moles of a

product P divided by the sum of all products visible in GC:


123

Molar fraction ¼ nPPnPi

� 100%: ð2Þ

It should be pointed out here that although guaiacol was

in some cases converted rapidly, the products were not

visible in chromatograms due to its oligomerisation. The

sum of the masses of the reactant and products in the liquid

phase (SMLP) determined by GC mass balance is defined

as follows:

SMLP ¼P

mGiþPii;Gm0;G

� 100% ð3Þ

i.e. the sum of the masses of guaiacol and all products

visible in chromatograms at time t divided by the initial

mass of guaiacol.

3 Results and Discussion

3.1 Catalyst Characterization Results

The BET specific area of 40 wt% MoxC–SBA-15 equal to

340 m2/g is in the same range as reported for 30 wt%

Mo2C–SBA-15, which exhibited BET surface area of

403 m2/g [29]. The BET for the parent SBA-15 was

645 m2/g. MoxC–SBA-15 was composed of both 50 wt%

Mo2C and 50 wt% MoC phases, with MoC exhibiting

peaks at 36.4�, 42.3�, 61.3� corresponding to (111), (200)and (220) faces [36] as denoted in XRD results (Fig. 1).

TEM images of the fresh and spent 40 wt% MoxC–

SBA-15 catalysts used in guaiacol HDO at 200 �C and300 �C under 30 bar showed no sintering with the averagecrystallite particle sizes for both materials being in the

range of 6.1–7.3 nm (Fig. 2). In the fresh 40 wt% MoxC–

SBA-15 catalysts some separate clusters with the size of

140 nm outside SBA-15 matrix are visible, but their

amount decreased in the spent catalyst, which was also

indicated by energy-dispersive X-ray analysis (EDXA)

analysis giving Mo/Si ratio (discussed below).

The fresh and spent 5 wt% Pt/C catalysts contained well

dispersed spherical Pt particles with the average particle

size of 3.1 and 3.2 nm, respectively indicating absence of

sintering (Table 3; Fig. 3).

EDXA results showed that the Mo/Si mass ratio

decreased from the fresh 40 wt% MoxC–SBA-15 from 1.0

to 0.88 when the catalyst was used in guaiacol HDO at

300 �C (Table 3). This might indicate that a part ofmolybdenum was removed from the catalyst by leaching.

Thermogravimetry is one of the methods to investigate

coke on the catalyst surface. Analysis of the spent Ru/C

catalyst used in guaiacol HDO in [8] demonstrated maxi-

mally 35% weight loss from the spent catalyst in the

temperature range of 100–1000 �C when the weight lossfrom the fresh catalyst was subtracted. In the current work

the weight losses between 100 and 900 �C for the fresh andspent 40 wt% MoxC–SBA-15 used in guaiacol transfor-

mation at 200 �C and 300 �C were 3, 39 and 8%, respec-tively, clearly showing that especially at 200 �C asubstantial amount of organic compounds was accumulated

on the catalyst surface (Fig. 4a). In this case the catalyst

was not very active, which will be further elaborated.

A commercial 5 wt% Pt/C (Degussa) was tested in this

work for comparison. The metal dispersion and the cluster

size were 36.2% and 3 nm, respectively. The catalyst is

slightly acidic as pH of the catalyst slurry is 5.6 [37]. The

weight loss from the fresh 5 wt% Pt/C catalyst, which

contains also water release, is 14% in the temperature

range between 100 and 900 �C, being 34% for the spent5 wt% Pt/C catalyst applied in guaiacol transformation at

300 �C under 30 bar (Fig. 4).

0 2 4 6 8 10

0

200

400

600

800

1000

1200

1400

1600

1800

Inte

nsity

(a.u

.)

2 Theta (o)5 10 15 20 25 30 35 40 45 50 55 60 65 70

0

2

4

o

o

o

o

o

o

o

o

o

*

*

*

**

***

Inte

nsity

(a.u

.)

2 Theta (°)

o

(a) (b)

Fig. 1 Diffractograms of a SBA-15 and b 40 wt% MoxC–SBA-15. Notation: (asterisks) Mo2C and (open circles) MoC phases. The diffractionpeaks of Mo2C and MoC have been taken from PDFs 71-0242 and 89-4305, respectively


123

In this work coke was extracted from the spent catalysts

used in guaiacol transformation at 200 �C under totalpressure of 30 bar hydrogen with refluxing heptane for 4 h

and analyzed by SEC (Fig. 5). The amount of extracted

oligomers from the spent 40 wt% MoxC–SBA-15 was

high. When comparing the peaks in SEC chromatogram

with the reference (polystyrene), it can be stated that the

main oligomers over MoxC–SBA-15 contained mostly

more than nine and five monomeric units.

a

5 10 150

20

40

60

80

100

120

140

160

180

Size Range (nm)

Freq

uenc

y

b

c

5 10 150

20

40

60

80

100

120

140

160

180

Size range (nm)

Freq

uenc

y

d

e

5 10 15 200

20

40

60

80

100

120

140

160

180

Size range (nm)

Freq

uenc

y

f

Fig. 2 Transmission electron microscopy images and histograms ofthe fresh (a and b), the spent (c and d) 40 wt% MoxC–SBA-15catalysts in the reaction of guaiacol at 200 �C under total pressure of

30 bar and 40 wt% MoxC–SBA-15 catalysts (e and f) in the reactionof guaiacol at 300 �C under total pressure of 30 bar. The scale bar is100 nm


123

Extensive coking of MoxC–SBA-15 can be explained by

high temperature used in the current work for deoxygena-

tion of guaiacol. Furthermore, the main product was ben-

zene (see below). Demethoxylation and reductive

hydroxylation can thus lead to catalyst coking.

3.2 Thermodynamic Analysis of GuaiacolHydrodeoxygenation

In order to reveal thermodynamic consistency of the

experimentally observed results calculations of the Gibbs

Table 3 Characterization results of the fresh and spent catalysts

Catalyst Metal particle size TEM (nm) Specific surface area (m2/gcat.) Phases (XRD) Mo/Si ratio (SEM–EDXA)

Fresh Spent Fresh Spent

40 wt% Mo2C–SBA-15 7.3 6.1b 340 Mo2C, MoC Mo/Si = 1.0 Mo/Si = 0.88

b

7.0c

5 wt% Pt/C 3.1 3.2a 916 n.d. n.d. n.d.

n.d. Not determinedaFrom the spent catalyst used in guaiacol transformation at 300 �CbFrom the spent catalyst used in guaiacol transformation at 200 �CcFrom the spent catalyst used in guaiacol transformation at 200 �C

b

d

0

200

400

600

800

1000

3 6 9Fr

eque

ncy

Size range

0100200300400500600700800900

1000

3 6 9

Freq

uenc

y

Size range, nm

a

c

Fig. 3 Transmission electron microscopy images and histograms of the fresh (a and b) and spent (c and d) 5 wt% Pt/C catalysts in the reaction ofguaiacol at 300 �C under 30 bar total pressure. The scale bar is 50 nm


123

free energy changes were made. Enthalpy (DH0r ) and Gibbsfree energy (DG0r ) at standard conditions were calculatedby following a thermodynamic approach, starting from the

standard enthalpy (DH0f ) and Gibbs free energy (DG0f ) of

formation from the elements derived from the database

included in ChemCAD v.5.0 [38],

DH0r;j ¼X

j

mi;j � DH0f ;i; ð4Þ

DG0r;j ¼X

j

mi;j � DG0f ;i: ð5Þ

The equilibrium constant of each reaction was calcu-

lated from its definition,

K0j ¼ exp �DG0r;iRT

!

: ð6Þ

The dependence of the reaction free Gibbs energy on

temperature was included by implementing the Gibbs–

Helmholtz equation valid at P = 1 bar (DGUr;j).

DGUr;jðTÞT

¼DG0r;jT0

þ DH0r;j1

T� 1T0

� �

: ð7Þ

Finally, to calculate the DGr,j at different pressures, thefollowing equation was implemented.

DGr;jðPÞ ¼ DGUr;j þ nRT lnP

P0

� �

: ð8Þ

The calculated enthalpy and Gibbs free energy forma-

tion for each component are reported in Table 4. The data

were retrieved from ChemCAD v.5.0 database directly.

Starting from these values, the enthalpy and Gibbs free

energy for each reaction (j) at standard conditions, equi-

librium constants at standard conditions (K0j ), enthalpy and

Gibbs free energy at different temperatures and pressure

were calculated. Two different temperatures were investi-

gated (T1= 473.15 K, T2= 573.15 K) and the energy values

were calculated also at P1= 25 bar.

The most feasible reaction is hydrogenation of guaiacol

to 2-methoxycyclohexanol in Table 4 (step 12) at 200 �Cunder 1 bar hydrogen followed by reductive dehydroxyla-

tion of cyclohexanol and 2-methoxycyclohexanol (steps 8

and 11). The effect of hydrogen pressure on Gibbs free

energy is clearly visible at both temperatures, i.e. the

reactions became less favorable with increasing hydrogen

pressure for all reactions. Hydrogenation of phenol and

0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

40 wt% Mo2C-SBA-15, Gua, 200°C

40 wt% Mo2C-SBA-15, Gua, 300°CM

ass

loss

(%)

Temperature (°C)

fresh

0 100 200 300 400 500 600 700 800 900

0

20

40

60

80

100

Pt/C guaiacol, 300oC

Mas

s lo

ss (%

)

Temperature (°C)

Pt/C fresh

(a) (b)

Fig. 4 Thermogravimetrical analysis (TGA) of the fresh and spent a 40 wt% MoxC–SBA-15 and b 5 wt% Pt/C

10 15 20 25

0

20000

40000

60000

80000

100000

120000

Inten

sity (

a.u)

Time (min)

Fig. 5 Size exclusionchromatogram (SEC) of the

extracted spent 40 wt% MoxC–

SBA-15. The catalyst was used

in guaiacol transformation at

200 �C under 30 bar totalpressure


123

benzene became also thermodynamically not feasible at

300 �C under 25 bar (steps 7, 3). Experimental determi-nation of 2-methoxycyclohexanone in the reaction at

300 �C under 30 bar total pressure in the current workagrees well with the thermodynamic calculations for step

10 showing that hydrogenation of 2-methoxycyclohex-

anone is not feasible at 300 �C under 25 bar. Table 4 alsoillustrates that alkylation of phenol with (step 4) is ther-

modynamically not feasibly, while there are no thermo-

dynamic restrictions for formation of cresol by

transalkylation of phenol with guaiacol.

3.3 Catalytic Results

Supported on SBA-15 molybdenum carbide was investi-

gated in guaiacol transformation at 200 �C under 30 bartotal pressure not, however, giving any products visible in

GC chromatograms. This indicates strong adsorption of

guaiacol on the catalyst surface as also confirmed by TGA

and SEC analysis. The sum of the masses of reactant and

products in the liquid phase determined by GC results was

therefore equal to zero (Table 5).

Supported 40 wt% MoxC–SBA-15 was at the same time

active at 300 �C giving the final conversion levels of 62%after 240 min (Table 5). The sum of the masses of the

reactant and products in the liquid phase determined by GC

for 40 wt% MoxC–SBA-15 was only 37%. When the solid

material determined in TGA was added to the sum of the

masses of the reactant and products in the liquid phase

determined by GC, it was still only 40%. These sums of the

masses of reactant and products in the liquid phase deter-

mined by GC contain only compounds visible in the GC

and the solid organic residue determined by TGA. In the

extraction of the spent catalyst 40 wt% MoxC–SBA-15

from guaiacol transformation at 200 �C large amounts ofoligomers were observed. The sum of the masses of the


obtained for molybdenum carbide catalyst supported on

SBA-15 in the current work in guaiacol transformation at

300 �C under 30 bar total pressure is lower than the onereported by Jongerius et al. [13], namely 72% at 350 �Cunder 55 bar of hydrogen over Mo2C/CNF. Higher sums of

the masses of the reactant and products in the liquid phase

determined by GC were reported in [2] in the range of

74–93% in guaiacol HDO in water as a solvent over Mo2C

supported on active carbon at 300 �C under 137 barhydrogen. It has been reported that the mass balance clo-

sure increases with increasing hydrogen pressure [13],

which is relatively low in the current work as compared to

[13].

Concentration dependencies for guaiacol HDO over

40 wt% MoxC–SBA-15 at 300 �C as well as selectivitydependence on conversion are given in Fig. 6. Guaiacol

transformation was very rapid already during heating of the

reaction mixture. Thereafter, the catalyst retained its

activity during the course of the reaction.

The main product in guaiacol transformation over

40 wt% MoxC–SBA-15 catalysts at 300 �C at the

Table 4 Enthalpy and Gibbs free energy for each reaction (j) (reaction numbers are shown in Scheme 1) at standard conditions, equilibriumconstants at standard conditions (K0j ), enthalpy and Gibbs free energy at different temperatures and pressures (T1 = 200 �C, T2 = 300 �C)

j DH0r;j (kJ/mol) DG0r;j (kJ/mol) K

0j DG

Ur;j (T1)

(kJ/mol)

DGUr;j (T2)(kJ/mol)

DGr,j (T1, P1)(kJ/mol)

DGr,j (T2, P1)(kJ/mol)

1 - 48.3 - 70.3 2.07 9 1012 - 83.2 - 90.6 - 70.6 - 75.3

2 - 62.5 - 66.3 4.15 9 1011 - 68.6 - 69.8 - 55.9 - 54.5

3 - 206 - 9.78 9 104 1.35 9 1017 - 34.3 19.3 - 21.7 17.3

4 45.9 5.18 9 104 8.56 9 10-10 55.2 57.2 67.9 72.5

5 - 66.3 - 7.47 9 104 1.21 9 1013 - 79.6 - 82.4 - 67.0 - 67.1

6 - 42.1 - 4.34 9 104 4.00 9 107 - 44.1 - 44.6 - 31.5 - 29.2

7 - 198 - 8.52 9 104 8.51 9 1014 - 19.0 18.8 - 0.635 34.2

8 - 70.4 - 78.9 9 104 6.57 9 1013 - 83.9 - 86.7 - 71.2 - 71.4

9 - 134 - 83.9 9 104 5.04 9 1014 - 54.3 - 37.4 - 41.7 - 22.1

10 - 41.5 1.88 4.69 9 10-1 27.4 41.9 40.0 57.3

11 - 70.4 - 73.5 7.46 9 1012 - 75.3 - 76.3 - 62.6 - 61.0

12 - 418 - 310 2.48 9 1054 - 248 - 212 - 235 - 196

13 - 77.2 - 81.5 1.87 9 1014 - 83.9 - 85.4 - 71.3 - 70.0

14 - 60.8 - 81.3 1.75 9 1014 - 93.4 - 100 - 80.7 - 84.9

15 - 192 - 82.2 2.52 9 1014 - 17.6 19.4 - 4.89 34.7

16 - 63.5 - 70.9 2.62 9 1012 - 75.2 - 77.7 - 62.5 - 62.3

17 - 48.7 - 62.1 7.50 9 1010 - 69.9 - 74.4 - 57.2 - 59.0


123

beginning of the reaction was benzene, whereas its selec-

tivity declined with increasing conversion and at the same

time selectivity to phenol increased (Fig. 6b). Formation of

phenol as the main product was also seen for Mo2C/CNF

[13]. On the other hand, cresol was the second major

product [13], whereas no cresol was obtained in the current

work over 40 wt% MoxC/SBA-15. Formation of cresol

requires transalkylation over acidic sites [39], which were

not detected in this catalyst by ammonia TPD (not shown).

Selectivity towards aromatic products, phenol, and

benzene decreased slightly from 94 to 86% during 4 h

reaction when selectivity to cyclohexanol was increasing to

a minor extent.

As a comparison to supported molybdenum carbide

guaiacol HDO was also investigated over 5 wt% Pt/C both

at 200 �C and 300 �C. Guaiacol reacted at 200 �C veryrapidly during heating of the reaction mixture, since its

conversion was already 19% after 1 min. The reaction rate

between 1 and 120 min was 0.02 mmol/min/gcat. after

which the catalyst was completely deactivated and the final

conversion remained at 46% level after 240 min (Fig. 7).

This result is in accordance with the literature [10],

reporting rapid guaiacol transformations at 250 �C with87% conversion over Pt/C under 30 bar hydrogen. For Pd/

silica alumina catalyst there was no conversion of guaiacol

at 200 �C under 30 bar hydrogen and this catalyst started toexhibit some activity at 230 �C. In addition, PtPd–Al–HMS(mesoporous aluminosilicate) was active in guaiacol HDO

surprisingly already at 200 �C under 50 bar hydrogen in3 h in methanol as a solvent giving 80% conversion [26].

This result is not directly comparative with the current

results due to the presence of methanol as a solvent and

lower pressure. Transformations of guaiacol at 300 �Cproceeded also very fast already during heating giving

conversion of 51% in 1 min (Fig. 8). After the first minute

the reaction rate was also very high, 0.06 mmol/min/gcat. in

the time range of 1 to 120 min. Noteworthy is also that

even after 240 min traces of guaiacol were visible in the

GC analysis indicating catalyst deactivation.

The sums of the masses of the reactant and products in

the liquid phase determined by GC obtained in guaiacol

transformation at 200 �C and 300 �C over 5 wt% Pt/Cwere 91% and 95%, respectively, reflecting minor

Table 5 Experimental results for guaiacol HDO

Catalysts T (�C) X SMLPa Sphenolb Scresol Sbenzene SIPB S2MCHOL S2MCHONE SMCH SCHOL SCH

Mo 200 0 0 0 0 0 0 0 0 0 0 0

Mo 300 62 37 15 0 71 0 0 0 0 4 10

Pt 200 46 91 0 0 0 0 81 0 2 15 3

Pt 300 98 95 0 0 0 0 69 26 0 5 0

IPB isopropylbenzene, 2MCHOL 2-methylcyclohexanol, 2MCHONE 2-methylcyclohexanone, MCH methylcyclohexane, CHOL cyclohexanol,

CH cyclohexaneaAt 60% conversionbSelectivity (mol%) refers to 50% conversion

(a) (b)

Fig. 6 HDO of guaiacol over 40 wt% MoxC–SBA-15 at 300 �Cunder 30 bar a concentration dependencies and b molar fraction ofproducts as a function of conversion. Symbols: guaiacol (filled

squares), phenol (filled triangles), benzene (filled circles), cyclohex-

anol (open squares), and cyclohexane (open circles)


123

accumulation of some organic materials on the catalyst

surface as also shown in TGA. When the sum of the masses

of the reactant and products in the liquid phase determined

by GC in guaiacol transformation over 5 wt% Pt/C was

calculated taking into account both GC results from the

liquid phase and TGA results, the sum of the masses of the


was 100%. In addition, accumulation of organic material

was more prominent at lower temperature, being aligned

with the literature data on guaiacol transformation over

Mo2C/CNF catalyst [13]. For comparison, when Pt/C was

used as a catalyst at 250 �C the guaiacol conversion was87%, and only totally 80% of products were observed [10].

The main product in guaiacol transformation over

5 wt% Pt/C was 2-methoxycyclohexanol both at 200 �Cand 300 �C (Figs. 8, 9) analogously to the results in [10].

From the time dependent concentration profiles, it can

also be seen that deoxygenation occurs to a minor extent

since only low amounts of cyclohexane were formed.

Relatively large amounts of 2-methoxycyclohexanone were

formed at 300 �C, whereas this intermediate was not visi-ble at 200 �C. For formation of 2-methoxycyclohexanonetwo routes could be proposed, either starting from dehy-

drogenation of 2-methoxycyclohexanol or alternatively

directly from guaiacol via reversible hydrogenation–dehy-

drogenation analogously to phenol–cyclohexanone route

[40]. Experimental results show that as expected it is

thermodynamically more difficult to hydrogenate

2-methoxycyclohexanone at 300 �C compared to 200 �C.Consecutive reactions, such as hydrogenolysis of

2-methoxycyclohexanol were not occurring to a large

extent, which was also shown by thermodynamic analysis.

The molar fraction of 2-methoxycyclohexanol remained at

0 20 40 60 80 100 120 140 160 180 200 220 2400.000

0.005

0.010

0.015

Con

cent

ratio

n (m

ol/l)

Time (min)0 10 20 30 40

0

20

40

60

80

100

Mol

ar fr

actio

n (m

ol-%

)

Conversion %

(a) (b)

Fig. 7 Guaiacol transformation over 5 wt% Pt/C catalyst at 200 �Cunder 30 bar total pressure, a concentrations of different compoundsand b molar fraction as a function of guaiacol conversion, notation for

a and b guaiacol (filled squares), 2-methoxycyclohexanol (times),cyclohexane (open circles), 2-methoxycyclohexane (open squares),

cyclohexanol (filled circles)

0 60 120 180 240

0.000

0.002

0.004

0.006

0.008

0.010

0.012

0.014

Con

cent

ratio

n (m

ol/l)

Time (min)

40 45 50 55 60 65 70 75 80 85 90 95 100

0

20

40

60

80

100

Mol

ar fr

actio

n (%

)

Conversion (%)

(a)(b)

Fig. 8 Guaiacol HDO over 5 wt% Pt/C at 300 �C under 30 bar totalpressure in hydrogen: a concentration profiles and b molar fraction ofproducts as a function of guaiacol conversion. Notation: guaiacol

(filled squares), phenol (filled triangles), cyclohexanol (open squares),

cyclohexane (open circles), methoxy-cyclohexanone (plus) and

2-methoxycyclohexanol (times) and 2-methoxycyclohexane

(asterisks)


123

a constant level of 80% at 200 �C with increasing con-version (Fig. 7), whereas at 300 �C it decreased onlyslightly giving cyclohexanol via demethoxylation (Fig. 8;

Scheme 1). At 200 �C selectivity to cyclohexanol was2-fold higher compared to 300 �C indicating thatdemethoxylation occurs already at relatively low temper-

atures. Moreover, only minor amounts of cyclohexane (few

%), a fully deoxygenated product, were formed over 5 wt%

Pt/C catalyst. It can be concluded that a mildly acidic

5 wt% Pt/C promotes mainly hydrogenation of the phenyl

ring thus consuming 3 mol of hydrogen per 1 mol of

guaiacol and producing as the main product the non-oxy-

genated 2-methoxycyclohexanol.

A similar reaction pathway as mentioned above was

observed for 40 wt% MoxC–SBA-15 catalysts at 300 �Cwhen guaiacol very fast gave a constant concentration of

benzene followed by a gradual transformation of guaiacol

to 2-methoxycyclohexanol. This part of the overall reaction

network can be thus essentially simplified leading to

Guaiacolads $ Guaiacol ! 2 - methoxycyclohexanone! 2 - methoxycyclohexanol:

ð9Þ

In Eq. (9) it is suggested that there is strong adsorption

of guaiacol on the catalyst forming some sort of its reser-

voir on the surface, which explains a lack of mass balance

closure in the liquid phase at the beginning of the reaction

and its increase when the reaction proceeds. In essence

hydrogenation of guaiacol to 2-methoxycyclohexanone and

2-methoxycyclohexanol shifts this equilibrium involving

strongly adsorbed guaiacol in favor of hydrogenation. At

the beginning of the reaction guaiacol concentration

decreased very rapidly giving benzene and strongly

adsorbed guaiacol. With increasing reaction time

2-methoxycyclohexanol started to be formed with

increasing the mass balance closure. The latter compound

displays a clear S-shaped behavior pointing out that

2-methoxycyclohexanone was formed as an intermediate.

The rates for this scheme are given as

rG!2MCHO ¼ qBkG!2MCHOcG; ð10Þr2MCHO!2MCHL ¼ qBk2MCHO!2MCHLc2MCHO; ð11ÞrG!Gads ¼ qBkG!GadscG; ð12ÞrGads!G ¼ qBkGads!GcGads; ð13Þ

where qB is the catalyst bulk density, G, Gads, 2MCHOand MCHL denote guaiacol, strongly adsorbed guaiacol,

2-methoxycyclohexanone and 2-methoxycyclohexanol.

The corresponding mass balances for each compound

are given as

dcG

dt¼ �rG!2MCHO � rG!Gads þ rGads!G; ð14Þ

dc2MCHO

dt¼ rG!2MCHO � r2MCHO!2MCHL; ð15Þ

dc2MCHL

dt¼ r2MCHO!2MCHL: ð16Þ

Because concentration of benzene did not change during

the reaction it was included in modelling only indirectly.

Namely the concentration of strongly adsorbed guaiacol

was calculated by subtracting concentration of benzene,

guaiacol, 2-methoxycyclohexanone and 2-methoxycyclo-

hexanol from the initial concentration of guaiacol. The

kinetic parameters were estimated using the backward

difference method as a subtask to the parameter estimation

with simplex and Levenberg–Marquardt methods imple-

mented in software ModEst [41]. The objective function

was defined as

h ¼X

yi � ŷið Þ2 ð15Þ

and the coefficient of determination R2 is defined as

Fig. 9 Comparison of experimental and calculated data for HDO ofguaiacol over 40 wt% MoxC–SBA-15 at 300 �C under 30 bar

Table 6 The estimated parameters for hydrogenation of guaiacol over40 wt% MoxC–SBA-15 at 300 �C under 30 bar

Parameter Estimate Standard error (%)

qBk2MCHO!2MCHL 0.0163 7.2

qBkG!2MCHO 0.0021 9.3

qBkGads!G 0.6 93

qBkG!Gads 60.5 84

Units of qBki are min-1


123

R2 ¼ 1 �P

ðyi � ŷiÞ2P

ðyi � �yiÞ2

ð16Þ

in which �yi is the mean value of observations and ŷi denotesmodel estimation. The calculated values of parameters

along with standard errors are given in Table 6.

The model fit is shown in Fig. 9, illustrating a good

overall description, which also follows from the value of

the degree of explanation (97.22%).

4 Conclusions

Kinetics of guaiacol HDO was investigated in a batch

reactor using 40 wt% MoxC–SBA-15 and 5 wt% Pt/C

catalysts. Molybdenum carbide was prepared starting from

hexamethylenetetramine molybdate as a precursor com-

plex. Deposition of molybdenum carbide on SBA-15

resulted in both MoC and Mo2C phases and the specific

surface area of 340 m2/gcat. being more than 100-fold

higher than that for neat Mo2C. The average MoxC particle

size in the supported catalyst was 7.3 nm.

Thermodynamic calculations according to the Gibbs–

Helmholtz equation confirmed feasibility of guaiacol HDO

to phenol in the range of 200–300 �C, used for experi-ments. Exothermic hydrogenation reactions in the reactions

network being thermodynamically feasible at 200 �Cbecame unfeasible at higher temperatures.

A comparative investigation using 5 wt% Pt/C and

MoxC as catalysts clearly showed that a non acidic Pt/C

catalyst was very active giving 98% conversion of guaiacol

at 300 �C under 30 bar total pressure during 240 min. Themain product with 5 wt% Pt/C was 2-methoxycyclohex-

anol indicating that it is not a suitable catalyst for pro-

duction of hydrocarbons consuming also large amounts of

hydrogen during hydrogenation of the aromatic ring. At the

same time supported molybdenum carbide catalysts resul-

ted in formation of phenol, benzene and cyclohexane in the

liquid phase. Kinetic modelling was done quantitatively

describing the concentration dependences with time.

Acknowledgements Open access funding provided by Abo AkademiUniversity (ABO). Lenka Pelı́šková is acknowledged for performing

XRD measurements.

Open Access This article is distributed under the terms of the CreativeCommons Attribution 4.0 International License (http://creative

commons.org/licenses/by/4.0/), which permits unrestricted use, dis-

tribution, and reproduction in any medium, provided you give

appropriate credit to the original author(s) and the source, provide a

link to the Creative Commons license, and indicate if changes were

made.

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Kinetic and Thermodynamic Analysis of Guaiacol HydrodeoxygenationAbstractGraphic Abstract IntroductionExperimentalCatalyst Characterization MethodsCatalytic Tests and Analysis of Reaction Mixture

Results and DiscussionCatalyst Characterization ResultsThermodynamic Analysis of Guaiacol HydrodeoxygenationCatalytic Results

ConclusionsAcknowledgementsReferences

kinetic and thermodynamic analysis of guaiacol hydrodeoxygenation … · 2019. 7. 4. · kinetic...

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